EP4547735A1 - Polysiloxane filler treating agent and composition prepared therewith - Google Patents

Polysiloxane filler treating agent and composition prepared therewith

Info

Publication number
EP4547735A1
EP4547735A1 EP23761400.3A EP23761400A EP4547735A1 EP 4547735 A1 EP4547735 A1 EP 4547735A1 EP 23761400 A EP23761400 A EP 23761400A EP 4547735 A1 EP4547735 A1 EP 4547735A1
Authority
EP
European Patent Office
Prior art keywords
composition
range
treating agent
filler
independently
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23761400.3A
Other languages
German (de)
French (fr)
Inventor
Hai Wang
Matthew Carter
Hongyun XU
Dan Zhao
Elena C. MONTOTO-BLANCO
Tzu-Chi Kuo
Eric Joffre
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Rohm and Haas Co
Dow Silicones Corp
Original Assignee
Dow Global Technologies LLC
Rohm and Haas Co
Dow Silicones Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies LLC, Rohm and Haas Co, Dow Silicones Corp filed Critical Dow Global Technologies LLC
Publication of EP4547735A1 publication Critical patent/EP4547735A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the present invention relates to a polysiloxane-based filler treating agent and its application in thermally conductive formulations.
  • thermally conductive formulations that provide more uniform and more efficient heat dissipation from integrated circuits, battery packs, microelectronic circuitry, and electric motors.
  • the major components of conventional thermally conductive formulations are a matrix polymer, inorganic filler particles, and a filler treating agent (FT A).
  • FT A filler treating agent
  • the inorganic particles are the least expensive component in a thermally conductive formulation and provide heat dissipation. It is desirable, therefore, to load and uniformly disperse high levels of filler particles into the matrix polymer; uniform dispersion is challenging, however, because the filler particles are generally incompatible with the matrix polymer, resulting in phase separation.
  • FTAs which have chemical functionalities compatible with both the matrix polymer and the filler particles promote compatibility and improve the dispers ability of filler particles with the matrix by associating with the surface of the inorganic particles.
  • Examples of commercially available FTAs are monotrimethoxysilyloxy-terminated polydimethylsiloxanes, represented by the following formula:
  • the present invention addresses a need in the art by providing a composition comprising: a) a polyorganosiloxane; b) filler particles; and c) a filler treating agent of Formula I:
  • each R 1 is independently Ci-Ce-alkyl, vinyl, phenyl, or benzyl; each R 1 is independently Ci-Ce-alkyl;
  • R 2 is: where r is from 0 to 5; s is 0 or 1; t is from 0 to 15; each R 3 is independently Ci-Ce-alkyl; a is an integer of 1 to 3; wherein the polyorganosiloxane has degree of polymerization in the range of from 40 to 800.
  • composition of the present invention is useful as a thermally conductive formulation.
  • the present invention is a composition
  • a composition comprising: a) a polyorganosiloxane; b) filler particles; and c) a filler treating agent of Formula I: where m is from 5 to 150; n is from 1 to 3; p is from 0 to 3; q is from 0 to 8; each R 1 is independently Cj-Ce-alkyl, vinyl, phenyl, or benzyl; each R 1 is independently Cj-Ce-alkyl;
  • R 2 is: where r is from 0 to 5; s is 0 or 1; t is from 0 to 15; each R 3 is independently Ci-Ce-alkyl; a is an integer of 1 to 3; and the dashed line represents the point of attachment to the alkylene group; wherein the polyorganosiloxane has degree of polymerization in the range of from 40 to 800.
  • the FTA of Formula I is a random copolymer; that is to say, the structural units with subscripts m, n, and p need not be in the order depicted in Formula I.
  • m is from 20 or from 50, to preferably 125; preferably, n is from 1 or from 1.5 or from 1.8, to 3 or to 2.5 or to 2.2; p is from 0 to 3 or to 2 or to 1 or to 0.5; q is from 1 or from 2 to 6 or to 4; each R 1 is preferably independently Ci-Ce-alkyl, more preferably methyl or ethyl, and most preferably methyl; R 3 is preferably methyl or ethyl, more preferably methyl; a is preferably 2 or 3, more preferably 3.
  • R 2 is represented by the following group: where t is 0 or 1 or 2 or 3.
  • R 2 is represented by the following group: where q + t is in the range of 0 or from 1 or from 3 or from 5, to 20 or to 14 or to 9.
  • the filler treating agent of the present invention may be prepared by contacting a compound of
  • the filler treating agent may also be prepared by contacting a compound of Formula Ic: where x is n + p; with a compound of Formula Id: in the presence of platinum catalyst and at advanced temperatures, to form a compound of Formula I, where s is 0 and y is from 0 to 25.
  • the polyorganosiloxane may be functionalized with, for example, one or more crosslinkable groups, such as terminal vinyl groups.
  • functionalized polyorganosiloxanes include monovinyl-di-Ci-Ce-alkyl terminated polysiloxane and bis(vinyl-di-Ci-Ce-alkyl) terminated polysiloxane, more particularly bis(vinyl-dimethyl) terminated polysiloxane, which can be prepared as described in US 4,329,273.
  • the filler particles are metal, metal oxide, metal hydrate, or ceramic nitride particles such as aluminum, aluminum oxide (alumina), aluminum trihydrate, boron nitride, or zinc oxide particles.
  • the D50 particle size of the filler particles is typically in the range of from 0.5 pm to 100 pm.
  • a multimodal (e.g., bimodal) distribution of first and second filler particles may be used in the formulation to boost filler particle concentration.
  • the polyorganosiloxane concentration is preferably in the range of from 1.9 or from 5 wt.% to
  • the FT A concentration is preferably in the range of from O.f or from 0.2 or from 0.3 wt.%, to 3 or to 1 or to 0.7 or to 0.5 wt.%, based on the weight of the composition; and the filler loading is preferably in the range of from 70 or from 80 or from 85 or from 90 wt.% to 98 or to 94 wt.%, based on the weight of the composition.
  • the formulated composition of the present invention has been found to have a favorable squeeze flow rate, viscosity, extrusion rate, and thermal conductivity.
  • NMR spectroscopy was performed using a Bruker Avance III HD 500 spectrometer equipped with a 5-mm Prodigy BBO CryoProbe (Billerica, MA). Proton spectra were acquired with a pulse repetition delay of 10 s. Chemical shifts are reported relative to the residual solvent protons of CDC13 (5 'H, 7.26 ppm).
  • a copolymer of Formula la' and a compound of Formula lb' were mixed at room temperature at a 1:1 molar ratio of vinyl to Si-H groups.
  • Karstedt’s catalyst (0.1 mol% based on vinyl groups) was added to the mixture and the temperature was elevated to 120 °C. After 2 h the mixture was allowed to cool to room temperature, after which time the reaction mixture was diluted with CHCh and filtered through activated charcoal/Celite. Volatile substances in the polymer solution were removed, and the product was characterized by SEC and NMR.
  • the formulated material was then hand-mixed, then mixed again at 1300 rpm for 30 s, then transferred to a glass jar and heated at 150 °C under vacuum for 1 h.
  • the total filler loading of the material was 85.3 wt.% and 69.7 vol%.
  • test formulation samples An oscillatory shear strain amplitude sweep was performed on the test formulation samples to characterize the formulation viscosity and the shear thinning behavior.
  • the test formulation samples are loaded onto the Anton Paar High Throughput Rheometer (AP HT Rheometer) using 25-mm parallel plate geometry. Trimming was performed at 1.0-mm gap with the automatic trimming robot. After a 300-s pre-test soaking time, the measurements were taken using the standard procedure of 10 rad/s oscillation frequency, sweeping from 0.01 to 300% strain amplitude with 20 sampling points per decade. Viscosity at 0.1% strain (low shear rate viscosity) was reported.
  • Extrusion rates were measured by loading the gel formulations into a 30-mL EFD syringe. The syringe was then attached to the EFD dispensing apparatus and material was dispensed at 55 Psi under nitrogen for 5 s. The extrusion rate was recorded as the mass dispensed during the 5-s dispensing period, as determined using an analytical balance.
  • Thermal conductivity was measured using a Hot Disk transient plane source tool (TPS 2500S) and a Kapton-encased thermal probe. Isotropic bulk measurements were performed on 6 mm diameter vessels.
  • Table 1 illustrates Squeeze flow (S.F, in mm), Viscosity @ 0.1% strain (Vise., in Pa-s) and Extrusion rate at 55 psi (E.R., in g/5 s) for the thermal gel samples.
  • RMS-759 refers to DOWSILTM RMS-759 Mono-trimethoxysiloxy-dimethylsiloxane Polymer (A Trademark of The Dow Chemical Company or its affiliates), which is the FTA used in Comparative Example 1.
  • the thermal conductivity of the all the formulations were measured at 2.3 W/m-K.
  • Examples 1-5 formulations exhibited acceptable squeeze flows, viscosities @ 0.1% strain, extrusion rates, and thermal conductivity. Extrusion rates were significantly improved as compared with the commercial formulation (Cl). The formulations of the present invention also benefit from the ease of preparation of the FTAs.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

The present invention relates to a composition comprising: a) a polyorganosiloxane; b) filler particles; and c) a filler treating agent of Formula I: Formula I where R1, R2, m, n, p, and q are as defined herein. The composition is useful as a thermally conductive formulation.

Description

Polysiloxane Filler Treating Agent and Compositions Prepared Therewith
Background of the Invention
The present invention relates to a polysiloxane-based filler treating agent and its application in thermally conductive formulations.
Increased demand for conductive composite materials is driving the discovery of thermally conductive formulations that provide more uniform and more efficient heat dissipation from integrated circuits, battery packs, microelectronic circuitry, and electric motors. The major components of conventional thermally conductive formulations are a matrix polymer, inorganic filler particles, and a filler treating agent (FT A). The inorganic particles are the least expensive component in a thermally conductive formulation and provide heat dissipation. It is desirable, therefore, to load and uniformly disperse high levels of filler particles into the matrix polymer; uniform dispersion is challenging, however, because the filler particles are generally incompatible with the matrix polymer, resulting in phase separation. FTAs, which have chemical functionalities compatible with both the matrix polymer and the filler particles promote compatibility and improve the dispers ability of filler particles with the matrix by associating with the surface of the inorganic particles. Examples of commercially available FTAs are monotrimethoxysilyloxy-terminated polydimethylsiloxanes, represented by the following formula:
(See US 7,592,383 B2, column 6). Unfortunately, while this class, as well as other structurally similar FTAs are high performing, they are extremely costly because they are prepared by multistep synthetic procedures that require the use of toxic reagents and solvents, and a host of purification steps. It would therefore be an advantage in the art of compatibilizing agents for thermally conductive formulations to discover a relatively low-cost FT A that has acceptable performance properties, including squeeze flow, extrusion rate, and viscosity. Summary of the Invention
The present invention addresses a need in the art by providing a composition comprising: a) a polyorganosiloxane; b) filler particles; and c) a filler treating agent of Formula I:
I where m is from 5 to 150; n is from 1 to 3; p is from 0 to 3; q is from 0 to 8; each R1 is independently Ci-Ce-alkyl, vinyl, phenyl, or benzyl; each R1 is independently Ci-Ce-alkyl;
R2 is: where r is from 0 to 5; s is 0 or 1; t is from 0 to 15; each R3 is independently Ci-Ce-alkyl; a is an integer of 1 to 3; wherein the polyorganosiloxane has degree of polymerization in the range of from 40 to 800.
The composition of the present invention is useful as a thermally conductive formulation. Detailed Description of the Invention
The present invention is a composition comprising: a) a polyorganosiloxane; b) filler particles; and c) a filler treating agent of Formula I: where m is from 5 to 150; n is from 1 to 3; p is from 0 to 3; q is from 0 to 8; each R1 is independently Cj-Ce-alkyl, vinyl, phenyl, or benzyl; each R1 is independently Cj-Ce-alkyl;
R2 is: where r is from 0 to 5; s is 0 or 1; t is from 0 to 15; each R3 is independently Ci-Ce-alkyl; a is an integer of 1 to 3; and the dashed line represents the point of attachment to the alkylene group; wherein the polyorganosiloxane has degree of polymerization in the range of from 40 to 800.
The FTA of Formula I is a random copolymer; that is to say, the structural units with subscripts m, n, and p need not be in the order depicted in Formula I. Preferably m is from 20 or from 50, to preferably 125; preferably, n is from 1 or from 1.5 or from 1.8, to 3 or to 2.5 or to 2.2; p is from 0 to 3 or to 2 or to 1 or to 0.5; q is from 1 or from 2 to 6 or to 4; each R1 is preferably independently Ci-Ce-alkyl, more preferably methyl or ethyl, and most preferably methyl; R3 is preferably methyl or ethyl, more preferably methyl; a is preferably 2 or 3, more preferably 3.
In one aspect, R2 is represented by the following group: where t is 0 or 1 or 2 or 3.
In another aspect, R2 is represented by the following group: where q + t is in the range of 0 or from 1 or from 3 or from 5, to 20 or to 14 or to 9.
The filler treating agent of the present invention may be prepared by contacting a compound of
Formula la: where x is n + p; with a compound of the following formula lb: in the presence of platinum catalyst and at advanced temperatures, to form a compound of Formula I, where R2 is:
The filler treating agent may also be prepared by contacting a compound of Formula Ic: where x is n + p; with a compound of Formula Id: in the presence of platinum catalyst and at advanced temperatures, to form a compound of Formula I, where s is 0 and y is from 0 to 25.
The polyorganosiloxane may be functionalized with, for example, one or more crosslinkable groups, such as terminal vinyl groups. Examples of such functionalized polyorganosiloxanes include monovinyl-di-Ci-Ce-alkyl terminated polysiloxane and bis(vinyl-di-Ci-Ce-alkyl) terminated polysiloxane, more particularly bis(vinyl-dimethyl) terminated polysiloxane, which can be prepared as described in US 4,329,273.
The filler particles are metal, metal oxide, metal hydrate, or ceramic nitride particles such as aluminum, aluminum oxide (alumina), aluminum trihydrate, boron nitride, or zinc oxide particles. The D50 particle size of the filler particles, as determined using a HELOS laser diffraction device, is typically in the range of from 0.5 pm to 100 pm. A multimodal (e.g., bimodal) distribution of first and second filler particles may be used in the formulation to boost filler particle concentration.
The polyorganosiloxane concentration is preferably in the range of from 1.9 or from 5 wt.% to
15 or to 10 wt.% based on the weight of the composition; the FT A concentration is preferably in the range of from O.f or from 0.2 or from 0.3 wt.%, to 3 or to 1 or to 0.7 or to 0.5 wt.%, based on the weight of the composition; and the filler loading is preferably in the range of from 70 or from 80 or from 85 or from 90 wt.% to 98 or to 94 wt.%, based on the weight of the composition.
The formulated composition of the present invention has been found to have a favorable squeeze flow rate, viscosity, extrusion rate, and thermal conductivity.
Examples
Size Exclusion Chromatography Method
SEC separations were performed on a liquid chromatograph with an Agilent 1260 Infinity II isocratic pump, multicolumn thermostat, integrated degasser, autosampler, and refractive index detector. The system was equipped with two PLgel Mixed A columns (300 x 7.5 mm i.d., particle size = 20 pm) and a guard column (50 x 7.5 mm i.d.). The column oven and the refractive index detector operated at 40 °C. The sample injection volume was 100 pL and separations were performed with THE as the eluent at a flow rate of 1.0 mL/min. The instrument was calibrated with ten narrow-dispersity polystyrene standards from 580 - 371,000 Da. Data analysis was carried out using the Agilent GPC/SEC software package version A.02.01 (Build 9.34851).
NMR Spectroscopy Method
NMR spectroscopy was performed using a Bruker Avance III HD 500 spectrometer equipped with a 5-mm Prodigy BBO CryoProbe (Billerica, MA). Proton spectra were acquired with a pulse repetition delay of 10 s. Chemical shifts are reported relative to the residual solvent protons of CDC13 (5 'H, 7.26 ppm).
Example A - Preparation of Filler Treating Agent
A copolymer of Formula la' and a compound of Formula lb' were mixed at room temperature at a 1:1 molar ratio of vinyl to Si-H groups. Karstedt’s catalyst (0.1 mol% based on vinyl groups) was added to the mixture and the temperature was elevated to 120 °C. After 2 h the mixture was allowed to cool to room temperature, after which time the reaction mixture was diluted with CHCh and filtered through activated charcoal/Celite. Volatile substances in the polymer solution were removed, and the product was characterized by SEC and NMR.
Example B - Preparation of Filler Treating Agent
The copolymer of Formula Ic' and the compound of Formula Id' were mixed at room temperature at a 1:1 molar ratio of vinyl to Si-H groups and the reaction, workup, and characterizations were carried out as described in Example A. Examples C, D, E - Preparation of Filler Treating Agents
The compound of Formula le' and Formula lb' were mixed at room temperature at 3:1, 3:2, and 1 :1 mole-to-mole ratios of vinyl to Si-H groups to prepare Examples C, D, and E.
Examples 1-5 and Comparative Example 1 - Preparation of Formulations containing an FTA
Formulations were prepared by combining the FTA (0.23 g) with DOWSIL™ 2-7287 Vinyl dimethyl terminated poly dimethylsiloxane (5.31 g, viscosity = 80 cP, A Trademark of The Dow Chemical Company or its Affiliates) and DOWSIL™ CV-119 Vinyl dimethyl terminated polydimethylsiloxane (1.79 g, viscosity = 450 cP) in a Max- 10 mixer cup and mixing at a speed of 2000 rpm for 30 s. This blend was then combined with SB 36 Alumina Trihydrate (7.07 g, D50 = 25 pm) in a Max-40 mixer cup and mixed at a speed of 1300 rpm for 30 s. Maxfil MX200 Alumina Trihydrate (35.57 g, D50 = 45 pm) was added to the formulation and mixed at a speed of 1300 rpm for 30 s. The formulated material was then hand-mixed, then mixed again at 1300 rpm for 30 s, then transferred to a glass jar and heated at 150 °C under vacuum for 1 h. The total filler loading of the material was 85.3 wt.% and 69.7 vol%.
Measurement of Squeeze Flow
A squeeze-flow test was used to characterize the flowability of the test formulations containing FTA samples as follows: The thermally conductive test formulation (0.6 g) was sandwiched between two glass slides (25 x 7 5 x 1.0 mm, obtained from Thermofisher) and separated by two 1-mm shims to control the thickness. The top glass slide was manually pressed down to ensure a uniform spread of the material, and the initial diameter of the material was recorded as Di. The 1-mm spacers were then removed from the test sample, and a 350-g mass was placed on the top glass and allowed to stand for 1 min. The post-squeeze diameter was recorded as D2 and the squeeze flow was calculated as AR = (D2 - Di)/2 (mm).
Measurement of Viscosity at 0.1% Strain
An oscillatory shear strain amplitude sweep was performed on the test formulation samples to characterize the formulation viscosity and the shear thinning behavior. The test formulation samples are loaded onto the Anton Paar High Throughput Rheometer (AP HT Rheometer) using 25-mm parallel plate geometry. Trimming was performed at 1.0-mm gap with the automatic trimming robot. After a 300-s pre-test soaking time, the measurements were taken using the standard procedure of 10 rad/s oscillation frequency, sweeping from 0.01 to 300% strain amplitude with 20 sampling points per decade. Viscosity at 0.1% strain (low shear rate viscosity) was reported.
Measurement of Extrusion Rate
Extrusion rates were measured by loading the gel formulations into a 30-mL EFD syringe. The syringe was then attached to the EFD dispensing apparatus and material was dispensed at 55 Psi under nitrogen for 5 s. The extrusion rate was recorded as the mass dispensed during the 5-s dispensing period, as determined using an analytical balance. Thermal conductivity Measurements
Thermal conductivity was measured using a Hot Disk transient plane source tool (TPS 2500S) and a Kapton-encased thermal probe. Isotropic bulk measurements were performed on 6 mm diameter vessels.
Table 1 illustrates Squeeze flow (S.F, in mm), Viscosity @ 0.1% strain (Vise., in Pa-s) and Extrusion rate at 55 psi (E.R., in g/5 s) for the thermal gel samples. RMS-759 refers to DOWSIL™ RMS-759 Mono-trimethoxysiloxy-dimethylsiloxane Polymer (A Trademark of The Dow Chemical Company or its Affiliates), which is the FTA used in Comparative Example 1. The thermal conductivity of the all the formulations were measured at 2.3 W/m-K.
Table 1 - Properties of Thermal Gel Samples
Examples 1-5 formulations exhibited acceptable squeeze flows, viscosities @ 0.1% strain, extrusion rates, and thermal conductivity. Extrusion rates were significantly improved as compared with the commercial formulation (Cl). The formulations of the present invention also benefit from the ease of preparation of the FTAs.

Claims

Claims:
1. A composition comprising: a) a polyorganosiloxane; b) filler particles; and c) a filler treating agent of Formula I:
I where m is from 5 to 150; n is from 1 to 3; p is from 0 to 3; q is from 0 to 8; each R1 is independently Ci-Ce-alkyl, vinyl, phenyl, or benzyl; each R1 is independently Ci-Ce-alkyl;
R2 is: where r is from 0 to 5; s is 0 or 1; t is from 0 to 15; each R3 is independently Ci-Ce-alkyl; a is an integer of 1 to 3; wherein the polyorganosiloxane has degree of polymerization in the range of from 40 to 800.
2. The composition of Claim 1 wherein, based on the weight of the composition, the concentration of the polyorganosiloxane is in the range of from 1.9 to 15 wt.%, the concentration of the filler particles is in the range of from 70 to 98 wt.%, and the concentration of the filler treating agent of Formula 1 is in the range of from 0.1 to 3 wt%; wherein the filler particles are aluminum, alumina, aluminum trihydrate, boron nitride, or zinc oxide particles.
3. The composition of Claim 2 wherein each R1 is independently Ci-C>, -alkyl; p is from 0 to 2; q is from 2 to 4; each R1 is independently Ci-Ce-alkyl; and a is 2 or 3; wherein the filler particles are alumina particles at a concentration in the range of from 85 to 94 wt%, based on the weight of the composition.
4. The composition of Claim 3 wherein each R1 is independently methyl or ethyl; and p is 0 or 1.
5. The composition of Claim 4 wherein each R1 is methyl; m is from 50 to 125; n is from 1.8 to 2.2; each R3 is methyl; and p is from 0 to 0.5; wherein the alumina filler particles are present as a bimodal distribution of first alumina filler particles and second alumina filler particles.
6. The composition of any of Claims 1 to 5, where n is 2 and R2 is represented by: where t is 0 or 1 or 2 or 3 ; and p is 0.
7. The composition of Claim 6 wherein t is 0; and each R3 is methyl.
8. The composition of any of Claims 1 to 5 where n is 2 and R2 is represented by: where q + t is in the range of 0 to 20; and p is 0.
9. The composition of Claim 8 where q + 1 is in the range of from 3 to 14.
10. The composition of Claim 8 where q + t is in the range of from 5 to 9.
EP23761400.3A 2022-08-08 2023-08-04 Polysiloxane filler treating agent and composition prepared therewith Pending EP4547735A1 (en)

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US202263396030P 2022-08-08 2022-08-08
PCT/US2023/071640 WO2024036080A1 (en) 2022-08-08 2023-08-04 Polysiloxane filler treating agent and composition prepared therewith

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US4329273A (en) 1978-03-07 1982-05-11 General Electric Company Self-bonding silicone rubber compositions
JP4587636B2 (en) 2002-11-08 2010-11-24 東レ・ダウコーニング株式会社 Thermally conductive silicone composition
EP3688097B1 (en) * 2017-09-29 2024-05-15 Dow Silicones Corporation Silicone composition comprising filler
WO2021109051A1 (en) * 2019-12-05 2021-06-10 Dow Silicones Corporation Highly thermally conductive flowable silicone composition

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